STUDY OF CALCIUM SULFATE SCALING INDEX TENDENCY LEMIGAS SCIENTIFIC CONTRIBUTIONS

TJUWATI MAKMUR VOL. 30. NO. 3, DECEMBER 2007 : 18 - 27

STUDY OF CALCIUM SULFATE SCALING INDEX

TENDENCY CALCULATIONS AT DIFFERENT
TEMPERATURE CONDITIONS IN INJECTION
WATER SAMPLES FROM OILFIELDS
by
Tjuwati Makmur

ABTRACT
Calcium sulfate scale is a type of scale found in petroleum industry and shows serious
problem, because it can plug pore media and cause a decrease in production rate.
Actual calcium sulfate (CaSO4) concentrations of S1, S2, S3 and S4 injection water
samples were in the range of 0.0208 to 0.4583 meq/l. While, the values of solubility of
S1, S2, S3 and S4 water samples at 77,145 and 1770F are in a range of 23.20 to 27.43
meq/l. Based on the results of calcium sulfate scaling tendency calculations showed that
the values of solubility of S1, S2, S3 and S4 water samples at various temperature condi-
tions (77,140 and 175 0F) are higher than actual CaSO 4 concentrations for the same
water samples. No occurrence of CaSO4 scale was found in all analyzed injection water
samples at different temperature conditions (77,140 and 1750F).
Key words : calcium sulfate scale, scaling index tendency calculation, solubility of injec-
tion water sample and actual CaSO4 concentration.

I. INTRODUCTION together of the Ca ions and tetrahedral SO4 groups.

Calcium sulfate scale has long been recognized The large calcium ions are packed between SO4
as one of the serious problems in oil and gas produc- groups, and dark areas are sulfur atoms (1,2,3).
tion leading to reduced production rates as flow be-
comes restricted.
Calcium sulfate scale is defined as the precipita-
tion of hard, adherent deposits of inorganic solid origi-
nating from aqueous media. This constitutes sulfate
of the alkaline earth metals calcium, barium and stron-
tium and complex salts of iron. Generally, the pro-
cess of the scale deposition occurs when the product
solubility of a compound considered is exceeded. The
main purpose of this study was firstly, to determine
chemical compositions of four injection water samples
(S1, S2, S3 and S4). Secondly, to know calcium sul-
fate scaling index tendency calculations at various
temperatures (at 77,140 and 175oF) conditions in in-
jection water samples from the oilfield.
Figure 1
II. SRUCTURE AND NATURAL FORM OF Structure of anhydrite
ANHYDRITE
Source: Crystal structure of minerals, 1965,
The structure of anhydrite is a three dimensional Bell. G and Sons, Cornel University
view shown in Figure 1 and illustrates the packing

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STUDY OF CALCIUM SULFATE SCALING INDEX TENDENCY
TJUWATI MAKMUR
The natural form of anhydrite and clear gypsum
crystal with yellow sulfur band along bottom can be
seen Figures 2 and 3 below.
III. CaSO4 SOLUBILITY
Solubility of calcium sulfate scale is affected by
some factors(4,5,6), such as temperature, dissolved salts
content and pressure. The explanations are as fol-
lows:
A. Effect of temperature
Generally, gypsum is the stable form at low tem-
perature, whereas anhydrite is formed at higher tem-
Figure 2
Anhydrite (the natural form)
Source : Courtesy U.S. National Museum
Figure 2.3
Clear gypsum crystal with yellow sulfur
band along bottom
Source : Courtesy U.S. National Museum
LEMIGAS SCIENTIFIC CONTRIBUTIONS
VOL. 30. NO. 3, DECEMBER 2007 : 18 - 27
perature. Gypsum solubility increases with tempera-
ture up to about 40oC, then decreases with tempera-
ture as shown in Figure 4. This is quite different from
the temperature-solubility behaviour of CaCO3. Firstly,
gypsum is considerably more soluble than CaCO3 in
normal temperature range of interest. The solubility
of CaSO4 in distilled water is 2080 mg/l, while solu-
bility of CaCO3 in distilled water is 53 mg/l. Secondly,
the maximum in the gypsum curve explains that an
increase in temperature could either increase or de-
crease the solubility of gypsum depending on which
part of the temperature curve it is concerned with.
This is decidedly different from CaCO3 where an
Figure 4
Effect of temperature on calcium
sulfate solubility
Figure 5
Effect of NaCl on CaSO4 solubility
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STUDY OF CALCIUM SULFATE SCALING INDEX TENDENCY LEMIGAS SCIENTIFIC CONTRIBUTIONS
TJUWATI MAKMUR VOL. 30. NO. 3, DECEMBER 2007 : 18 - 27

increase in temperature always decreases the solu- C. Effect of pressure

bility. Note that above about 40 oC, anhydrite be- The solubility of calcium sulfate in water increases
comes less soluble than gypsum, so it could reason- with pressure. The effect of increased pressure is
ably be expected that anhydrite might be the pre- physical, resulting in a reduction in the size of the
ferred form of CaSO4 in deeper, hotter wells. Actu-
ally, the temperature at which the scale changes form
from gypsum to anhydrite or hemi-hydrate is a func-
tion of many factors, including dissolved salt content,
pressure, flow conditions and the speed at which dif-
ferent forms of CaSO4 can precipitate from solution.
The curve for the solubility of anhydrite inter-
sects the solubility curve for gypsum at 42oC. This is
transition point of gypsum-anhydrite. Above 100oC,
anhydrite will precipitate directly in a stirred or flow-
ing system. If the system is quiescent, hemi-hydrate
solubility becomes limiting. Conversion to anhydrite
could be expected with time.
B. Effect of dissolved salts
The presence of NaCl or dissolved salts other
than calcium or sulfate ions increases the solubility
of gypsum or anhydrite, up to a salt concentration of Figure 6
about 150,000 mg/l. Further increases in salt content Effect of pressure on concentration of
decrease CaSO4 solubility. This case is described in calcium sulfate
Figure 5 below.

Figure 7
Mechanism of the occurrence of calcium sulfate scale

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STUDY OF CALCIUM SULFATE SCALING INDEX TENDENCY LEMIGAS SCIENTIFIC CONTRIBUTIONS
TJUWATI MAKMUR VOL. 30. NO. 3, DECEMBER 2007 : 18 - 27

calcium sulfate molecule. Although rather large in-
creases in pressure are necessary to effect a signifi-
cant change in molecular size, the effect of pressure
can be important and beneficial in injection wells
where appreciable pressure may be developed. The
effect of pressure and temperature on anhydrite solu-
bility is shown in Figure 6.
IV. MECHANISM OF CaSO4 OCCURENCE
One of the most successful methods of second-
ary recovery is water flooding, a process in which
water is pumped down an injection well to flush or
remove oil from the formation as it moves along to a
producing well. The oil, along with the injected water
and connate water, is recovered at the well. Although

Table 1
The results of determination of chemical
compositions and ionic strength calculation
for S1 - injection water sample

Concentrations Ionic Strength Calculation

Ion
Conversion
(mg/l) Results
Factor
Na+ 772,10 2,20E-05 1,70E-02
++
Ca 12,86 5,00E-05 6,43E-04
++
Mg 2,85 8,20E-05 2,33E-04
-
Cl 356,78 1,40E-05 4,99E-03
CO3= 0,00 3,30E-05 0,00E+00
HCO3- 1240,78 8,20E-06 1,02E-02
SO4= 22,00 2,10E-05 4,62E-04
Figure 8 3,35E-02
The form of CaSO4 scale in pipe
Total Ionic Strength ( μ ) = 0,0335

Figure 9 Figure 10
Calcium sulfate scale on Large crystal of gypsum
meter-run screens produced from brine recovery operation

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TJUWATI MAKMUR VOL. 30. NO. 3, DECEMBER 2007 : 18 - 27

this method has been highly suc-

cessful and is in wide use today, Table 2
it is fraught with many problems. The results of caso4 scaling index tendency calculations
A major one is scale, such as cal- at Different temperature in S1 - injection water sample
cium sulfate scale (CaSO 4 ). Temp. o F K 4K
Scale is formed through several
77 1,89E-04 7,57E-04
stages :
140 1,89E-04 7,57E-04
1. mixture of water and dis-
175 1,54E-04 6,14E-04
solved salts.
Ion Concentrations Conversion M
2. solution.
(mg/l) Factor (moles/l)
3. supersaturation. ++
Ca 12,86 2,50E-05 3,22E-04
4. nucleation.
SO4= 22,00 1,05E-05 2,31E-04
5. crystal growth. X = ΔM = 9,05E-05
6. scale. S@ o
77 F = 27.43 m eq/l
Salts (such as NaCl, CaCl2 S @ 140 F = o
27.43 m eq/l
and NaSO4 etc ) are dissolved S @ 175 F =o
24.70 m eq/l
into water and the mixtures of Ion Concentrations Equivalent Concentrations
water and salts form solution. (mg/l) W eight (meq/l)
When the water as solvent can ++
Ca 12,86 20,00 0,6430
not dissolve the salts anymore, =
SO4 22,00 48,00 0,4583
this condition is called supersatu-
ration. Next stage is nucleation Actual CaSO 4 concentration = 0.4583 m eq/l
process, from time to time after S > actual , s o CaSO4 s cale is unlikely
nucleation process is followed by
crystal growth process. Last
stage is the occurrence of scale.
Generally, the process of the calcium sul-
fate scale deposition occurs when the product
solubility of a compound considered is ex- Table 3
The results of determination of chemical
ceeded. compositions and ionic strength calculation
Chemical reaction of the occurrence of for S2 - injection water sample
calcium sulfate scale can be written as fol-
Ionic Strength Calculation
lows: Concentrations
Ion Conversion
(mg/l) Results
2 2
Ca  SO 4  CaSO4 Factor
(aq) (aq) (solid)
Na+ 725,40 2,20E-05 1,60E-02
++
Mechanism of the formed calcium sulfate Ca 22,13 5,00E-05 1,11E-03
++
scale is described clearly in Figure 4.1. Mg 3,03 8,20E-05 2,48E-04
-
Some examples of calcium sulfate scale Cl 356,78 1,40E-05 4,99E-03
were found in the petroleum industry can be CO3= 24,05 3,30E-05 7,94E-04
seen in Figures 8, 9 and 10. HCO3 -
1197,99 8,20E-06 9,82E-03
=
SO4 8,00 2,10E-05 1,68E-04
V. METODOLOGY
3,31E-02
Solubility value for CaSO4 can be calcu- Total Ionic Strength ( μ ) = 0,0331
lated using the following equation values of Ksp
are known for the compound:

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TJUWATI MAKMUR VOL. 30. NO. 3, DECEMBER 2007 : 18 - 27

Solubility (meq/L) =
S = 1000 [(X2 + 4 Ksp) ½ - X] Table 4
The results of CaSO4 scaling index tendency calculations
Derivation of this equation at different temperature in S2 - injection water sample
follows the common ion effect.
The maximum solubility of a Temp. oF K 4K
slightly soluble salt is obtained 77 1,89E-04 7,54E-04
when the concentrations of the 140 1,89E-04 7,54E-04
cation and anion are equal. For 175 1,53E-04 6,12E-04
example : given s saturated so- Ion Concentrations Conversion M
lution of CaSO4 in water, where
(mg/l) Factor (moles/l)
the Ca+2 and SO4= concentrations
Ca ++ 22,13 2,50E-05 5,53E-04
are equal :
SO4= 8,00 1,05E-05 8,40E-05
Ca+2 concentration = S moles/
liter. X = Δ M = 4,69E-04
S@ 77 oF = 26.99 meq/l
SO4= concentration = S moles
S @ 140 oF = 26.99 meq/l
/ liter
o
S @ 175 F = 24.27 meq/l
Ksp = (S) (S) = S2
Ion Concentrations Equivalent Concentrations
S = (Ksp)1/2
(mg/l) Weight (meq/l)
The solubility of calcium sul- Ca ++ 22,13 20,00 1,1065
fate is equal to S moles/liter, SO4 =
8,00 48,00 0,1667
which is simply the square root
Actual CaSO4 concentration = 0.1667 meq/l
of the molar solubility product
S > actual , so CaSO4 scale is unlikely
constant.
However, in most natural
waters, the cation and anion con-
centration are not equal. In this
case, the difference between the two con-
centration is called the excess common ion Table 5
concentration. The presence of excess The results of determination of chemical
common ion reduces the solubility of the compositions and ionic strength calculation
for S3 - injection water sample
salt unless a complex ion or ion pair, such
as neutral magnesium sulfate, forms and Ionic Strength Calculation
Ion Concentrations
offsets the effect. For example: Conversion
(mg/l) Results
Ca+2 concentration = S moles/liter. Factor
SO4= concentration = S moles / liter Na + 559,70 2,20E-05 1,23E-02
In this case, the sulfate ion concentration Ca ++
12,89 5,00E-05 6,45E-04
as the larger of the two has been selected ++
Mg 3,52 8,20E-05 2,89E-04
randomly. The amount by which the sul-
-
fate ion concentration exceeds the calcium Cl 89,19 1,40E-05 1,25E-03
=
concentration, X, is the excess common ion CO3 24,05 3,30E-05 7,94E-04
concentration. HCO3 -
1210,22 8,20E-06 9,92E-03
Ksp = (S) (S + X) = S2 + SX SO =
1,00 2,10E-05 2,10E-05
4

The calcium sulfate solubility is equal 2,52E-02

to S moles/liter, since that is the maximum Total Ionic Strength ( μ ) = 0,0252
amount of calcium sulfate which can be
performed by combining S moles of Ca+2

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TJUWATI MAKMUR VOL. 30. NO. 3, DECEMBER 2007 : 18 - 27

with (S + X) moles of SO4=.

Rearranging : Table 6
The results of CaSO4 scaling index tendency
S2 + SX - Ksp = 0 calculations at different temperature
Taking the positive root of the qua- in S3 - injection water sample
dratic equation :
Temp. o F K 4K
for a divalent ion:
77 1,73E-04 6,91E-04
S (equiv./L) = (X2 + 4 Ksp)1/2 - X 140 1,73E-04 6,92E-04
or : 175 1,38E-04 5,53E-04
S (meq/L) = 1000 [X2 + 4 Ksp)1/2 Ion Concentrations Conversion M
– X] (mg/l) Factor (moles/l)

The ”actual concentration” of Ca++ 12,89 2,50E-05 3,22E-04

CaSO4 in solution is equal to the SO4= 1,00 1,05E-05 1,05E-05

smaller of the Ca+2 or SO4= concen- X = Δ M = 3,12E-04
trations (expressed in meq/liter) in the S@ 77oF = 25.97 meq/l
water of interest, since the smaller con- S @ 140oF = 25.99 meq/l
centration limits the amount of calcium S @ 17oF = 23.20 meq/l
sulfate which can be formed (4,5,7,8). Ion Concentrations Equivalent Concentrations
The calculated calcium sulfate (mg/l) Weight (meq/l)
++
solubility, S (meq/liter), is compared Ca 12,89 20,00 0,6445
with the actual concentration to de- SO4= 1,00 48,00 0,0208
termine if scale formation is likely. Actual CaSO4 concentration = 0.0208 meq/l
S > actual , so CaSO4 scale is unlikely
Case Summary

The water is saturated

S = Actual
with CaSO4.
The water is undersaturated
S > Actual with CaSO4. Table 7
Scale is unlikely. The results of determination of chemical
compositions and ionic strength calculation
The water is supersaturated
for S4 - injection water sample
S < Actual with CaSO4.
Scale is likely Ionic S tre ngth Ca lc ula tion
Conc e ntra ti
Ion
ons (m g/l) Conve rs ion
This formula can be used to calculate Re s ults
Fa c tor
the solubility of any divalent salt such as cal-
Na+ 5 7 8 ,9 0 2 ,2 0 E -0 5 1 ,2 7 E -0 2
cium sulfate (CaSO 4 ), barium sulfate
++
(BaSO4) or strontium sulfate (SrSO4). Ca 7 ,3 2 5 ,0 0 E -0 5 3 ,6 6 E -0 4
++
Mg 2 ,5 0 8 ,2 0 E -0 5 2 ,0 5 E -0 4
VI. RESULTS
C l- 1 6 9 ,4 7 1 ,4 0 E -0 5 2 ,3 7 E -0 3
Water analysis and calcium sulfate scal- =
C O3 1 2 ,0 2 3 ,3 0 E -0 5 3 ,9 7 E -0 4
ing index tendency calculations were focused
-
on four injection water samples, namely: S1, H C O3 9 1 0 ,7 2 8 ,2 0 E -0 6 7 ,4 7 E -0 3
S2, S3 and S4. Before injection water used S O 4= 1 1 ,0 0 2 ,1 0 E -0 5 2 ,3 1 E -0 4
as displacement fluid in water flooding pro- 2 ,3 8 E -0 2
cess process, initial stage must be carried
out, was water analysis. It plays important
To ta l Io n ic S tre n g th ( μ) = 0 ,0 2 3 8

role not only in water analysis, but also re-

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TJUWATI MAKMUR VOL. 30. NO. 3, DECEMBER 2007 : 18 - 27

lated to many factors, such as : water quality, injec- Table 6 ( for S3- water sample), Table 8 (for S4-
tion - formation water compatibility, water-rock com- water sample). Concentration of calcium (Ca+2) and
patibility, and even water flooding analysis. The re- sulfate (SO4=) ions in the water samples were tabu-
sults of laboratory water analysis gave valuable in- lated briefly in Table 9. All results of scaling index
formations, among of them, namely: tendency calculations at different temperature ( 77,
a. Type of cations and
anions were found
in water samples. Table 8
b. Concentrations of The results of CaSO4 Scaling index tendency calculations
at different temperature in S4 - injection water sample
cations and anions in
water samples.
Temp. oF K 4K
c. Which ions have po-
tential to form cal- 77 1,70E-04 6,79E-04
cium sulfate scaling 140 1,70E-04 6,80E-04
tendency.
175 1,36E-04 5,42E-04
The results of de-
termination of chemical Ion Concentrations Conversion M
compositions in the ana- (mg/l) Factor (moles/l)
lyzed water samples Ca ++ 7,32 2,50E-05 1,83E-04
were tabulated in =
SO4 11,00 1,05E-05 1,16E-04
Tables 1, 3, 5 and 7.
The obtained water X = ΔM = 6,76E-05
analysis data were used S @ 77 oF = 25.99 m eq/l
to calculate calcium sul- S @ 140 oF = 26.02 m eq/l
fate scaling tendency in o
S @ 175 F = 23.21 m eq/l
the water samples with
using equation as ex- Ion Concentrations Equivalent Concentrations
plained in Section V. (mg/l) Weight (meq/l)
The results of calcium ++
7,32 20,00 0,3662
Ca
sulfate scaling index
=
tendency calculations at SO4 11,00 48,00 0,2292
different temperature Actual CaSO4 concentration = 0.2292 m eq/l
conditions can be seen S > actual , s o CaSO4 s cale is unlikely
in Table 2 ( for S1-
water sample), Table 4
(for S2-water sample),

Table 9
Summary of the results of calcium and sulfate ions concentration determinations
in injection water samples (S1, S2, S3 and S4) from oilfield

Conce ntra tions of ions (m g/l) in Inje ction W a te r Sa m ple s

Ions
S1 S2 S3 S4
+2
Calcium (Ca ) 12,86 22,13 12,89 7,32
=
Sulfate (SO 4 ) 22,00 8,00 1,00 11,00

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TJUWATI MAKMUR VOL. 30. NO. 3, DECEMBER 2007 : 18 - 27

Table 10
Summary of the results of scaling index tendency calculations
at different temperature conditions in injection water samples from oilfield

Water Actual CaSO4

Solubility (meq/l) REMARKS
Sample Concentration (meq/l)

S1 S at 770F = 27.43 0,4583 S > actual CaSO4 scale was unlikely

S at 140 0F = 27.43 0,4583 S > actual CaSO4 scale was unlikely

S at 175 0F = 24.70 0,4583 S > actual CaSO4 scale was unlikely

S2 S at 77 0F = 26.99 0,1667 S > actual CaSO4 scale was unlikely

S at 140 0F = 26.99 0,1667 S > actual CaSO4 scale was unlikely

S at 175 0F = 24.27 0,1667 S > actual CaSO4 scale was unlikely

S3 S at 770F = 25.97 0,0208 S > actual CaSO4 scale was unlikely

S at 140 0F = 25.99 0,0208 S > actual CaSO4 scale was unlikely

S at 175 0F = 23.20 0,0208 S > actual CaSO4 scale was unlikely

S4 S at 770F = 25.99 0,2292 S > actual CaSO4 scale was unlikely

S at 140 0F = 26.02 0,2292 S > actual CaSO4 scale was unlikely

S at 175 0F = 23.21 0,2292 S > actual CaSO4 scale was unlikely

145 and 1770F) conditions in the injection water
samples from oilfield have been tabulated and sum-
marized in Table - 10 briefly. Generally, the values of
solubility of S1, S2, S3 and S4 water samples at vari-
ous temperature conditions (77, 140 and 1750F) were
in a range of 23.20 to 27.43 meq/l. While, actual
CaSO4 concentrations of S1, S2, S3 and S4 water
samples were in a range of 0.0208 to 0.4583 meq/l.
In this case, the values of solubility of S1, S2, S3 and
S4 water samples at certain temperature above are
higher than actual CaSO4 concentrations of the same
water samples. So, CaSO4 scale was unlikely or not
formed in S1, S2, S3 and S4 water samples at vari-
ous temperature conditions (77,140 and 1750F).
VII. CONCLUSIONS
All results of water analysis and calcium sulfate
scaling index tendency calculations have been ob-
tained and can be concluded as follows:
1. Based on the results of water analysis, concen-
trations of calcium ion (Ca+2) were in a range of
7.32 to 22.13 mg/l, and concentrations of sulfate
(SO4=) ion are in a range of 1 to 22 mg/l for S1,
S2, S3 and S4 injection water samples.
2. The results of calcium sulfate scaling index ten-
dency calculation indicated that the values of solu-
bility of S1, S2, S3 and S4 water samples at
77,145 and 1770F are in a range of 23.20 to 27.43
meq/l.
3. Actual CaSO4 concentrations of S1, S2, S3 and
S4 water samples were in a range of 0.0208 to
0.4583 meq/l.
4. The values of solubility of S1, S2, S3 and S4 wa-
ter samples at various temperature conditions
(77,140 and 1750F) are higher than actual CaSO4
concentrations for the same water samples.
5. CaSO4 scale was not formed in all analyzed in-
jection water samples at different temperature
conditions (77,140 and 1750F).

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TJUWATI MAKMUR
REFERENCES
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2. Jack, C.C. and Donald. J. W., 1976, “Water
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3. Johnson, K.S., 1983, “Water Scaling Problem in
the Oil Production Industry“, Chemicals in Oil In-
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4. Ostroff, A. G.., 1979, “Introduction to Oilfield Wa-
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of Corrosion Engineers, Houston, Texas, p.69-72.
LEMIGAS SCIENTIFIC CONTRIBUTIONS
VOL. 30. NO. 3, DECEMBER 2007 : 18 - 27
5. Case, L.C., 1977, “ Water Problems in Oil Pro-
duction “, 2 Edition, Tulsa, Oklahoma.
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27